JP7269247B2 - Hydrotreating catalyst for reduction of metals and sulfur in heavy oil - Google Patents

Description

(Related application)
This application claims the benefit of the priority filing date of US Provisional Patent Application No. 62/624,236, filed January 31, 2018, the disclosure of which is incorporated herein by reference.

(Field of Invention)
The present invention relates to hydroprocessing catalysts. More specifically, the present invention relates to hydroprocessing catalysts having trimetallic compositions and pore networks specifically designed for improved demetallization capabilities and sulfur removal.

Refineries tend to process more economical, heavier crudes containing an increased proportion of high boiling point components such as atmospheric and vacuum resids. These components contain high levels of sulfur, nitrogen, nickel, and vanadium, causing complications during downstream processing. In these applications, nickel and vanadium can take the form of porphyrin compounds, and removal of nickel is generally more difficult than removal of vanadium. Processing these heavier crudes to remove metals, sulfur and nitrogen and to saturate hydrocarbons is advantageous for several reasons. First, removal of sulfur and nitrogen allows compliance with environmental standards for downstream units. Second, removal of contaminant metals protects downstream unit catalysts such as those used in catalytic reformers, fluid catalytic cracking or isomerization units.

There have been ongoing efforts to develop hydrotreating catalysts with improved activity in terms of sulfur removal and demetallization. US Pat. No. 5,334,307 discloses a hydroprocessing catalyst having an amorphous porous refractory oxide support containing 2-8 weight percent silica. US Pat. No. 5,545,602 discloses an alumina support, a Group VIII non-noble metal oxide, a Group VI-B metal oxide, and 0-2 wt % phosphorus oxide. Nonetheless, there is a continuing need for hydroprocessing catalysts with improved activity and activity retention for sulfur metal removal, particularly nickel. It has been unexpectedly found that such improvements are possible using catalysts with specific trimetallic formulations and specifically designed pore structures.

The subject of the present disclosure relates to hydroprocessing catalysts having unique trimetallic formulations with specifically defined pore size distributions that provide exceptional sulfur metal removal activity, particularly with respect to nickel.

In one embodiment, the present disclosure provides a catalyst that includes a support and a metal component impregnated on the support. The support comprises alumina, the metal component comprises a first metal fraction and a second metal fraction, the first metal fraction comprising at least one metal selected from chromium, molybdenum, or tungsten. and the second metal fraction comprises at least two metals selected from cobalt, rhodium, iridium, nickel, palladium, or platinum. The catalyst has a first pore volume of 0.28 to 0.45 mL/g for pores with pore sizes of 12 nm to less than 16 nm, and 0 for pores of 2.0 nm to less than 12.0 nm. It has a secondary pore volume of 0.15-0.28 mL/g.

In another embodiment, the disclosure provides a process for producing a catalyst, including impregnating a metal component onto a support. The support comprises alumina and the metal component comprises a first metal fraction and a second metal fraction. The first metal fraction comprises at least one metal selected from chromium, molybdenum, tungsten, or mixtures thereof, and the second metal fraction comprises cobalt, rhodium, iridium, nickel, palladium, platinum, or It contains at least two different metals selected from mixtures thereof. The catalyst has a first pore volume of 0.28 to 0.45 mL/g for pores with pore sizes of 12 nm to less than 16 nm, and 0 for pores of 2.0 nm to less than 12.0 nm. It has a secondary pore volume of 0.15-0.28 mL/g.

For the purposes of this specification, the term "boehmite" or "pseudo-boehmite" refers to compounds of the formula Al ₂ O ₃ . These are used interchangeably, denoting a solid alumina material of H ₂ O and having an X-ray diffraction pattern showing a thick line coinciding with the main reflection of well-crystallized y-AlOOH.

The subject catalysts comprise a support and a metal component impregnated on the support and are designed to remove metals and sulfur from refinery sources. Sources include atmospheric retentate, vacuum retentate, or deasphalted oil, and can be obtained from crude oil. The type of crude oil or fraction of crude oil is not limited. Atmospheric retentate is the heavy oil fraction obtained by atmospheric distillation of crude oil and having a boiling point above 343°C. Distillation of atmospheric retentate under reduced pressure produces vacuum retentate, which is the heavy oil fraction boiling above 550°C. Deasphalted oil is the fraction obtained by removing the asphaltenes from the vacuum residue by solvent extraction. The catalysts described herein are preferably used to process feedstocks containing high levels of metals with high sulfur content, such as Middle East crude oil.

Catalysts prepared according to the present subject matter can be used under a wide range of reaction conditions, for example temperatures in the range of about 200-500° C., hydrogen pressures in the range of about ^5-300 bar, and liquid It can be used in a hydroprocessing process for processing multiple feeds with a space hourly space velocity (LHSV) of . The term "hydroprocessing" can encompass a variety of processes in which a hydrocarbon feedstock is reacted with hydrogen at elevated temperature and pressure (hydroprocessing reaction conditions), including hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetalization, hydrogen These include dearomatization, hydrocracking, and hydrocracking under mild pressure conditions (also called mild hydrocracking).

More specifically, the term "hydrotreating" as used herein refers to It refers to a petroleum refining process in which a petroleum feedstock (a complex mixture of hydrocarbons present in petroleum) is reacted under pressure with hydrogen in the presence of a catalyst. Hydrotreating includes hydrocracking and hydrotreating processes, which vary according to the amount of hydrogen reacted, the properties of the catalyst, and the nature of the petroleum feedstock being processed.

Hydrocracking is typically performed (a) at superatmospheric hydrogen partial pressures, (b) typically at temperatures below 593.3° C., and (c) with an overall net chemical consumption of hydrogen of and (d) in the presence of a solid supported catalyst containing at least one hydrogenation component, a predominantly hydrocarbon-based compound containing at least 5 carbon atoms per molecule ("feedstock") carried out. is understood to involve the hydrotreating of

Hydrotreating typically involves hydrotreating a predominantly hydrocarbon-based compound containing at least 5 carbon atoms per molecule (“feedstock”) for desulfurization and/or denitrification of the feedstock. Understood to include processing, processing (a) at superatmospheric hydrogen partial pressures, (b) at temperatures typically less than 593.3° C., and (c) the overall net chemical consumption of hydrogen and (d) in the presence of a solid supported catalyst containing at least one hydrogenation component.

catalyst carrier

The subject catalytic metals are contained in a perforated alumina support. The alumina used can be, for example, gamma alumina or a precursor of alumina such as boehmite or pseudoboehmite. The alumina may be peptized or unpeptized. Preferably, the alumina used in the preparation is peptized pseudoboehmite, which after mixing and forming is calcined to gamma alumina. Alumina compositions are typically prepared in batch processes in which the alumina is precipitated under controlled reactant concentrations and reaction conditions, including temperature, time, pH, reactant feed rates, and the like. Such processes are generally known in the art (e.g., Sanchez et al., US Pat. No. 4,154,812, Lussier et al., US Pat. No. 6,403,526, and references therein). See patents, the disclosures of which are incorporated herein by reference), and related alumina preparation methods are disclosed herein.

catalyst metal component

The catalytic metal component includes a first metal fraction and a second metal fraction. The first metal fraction comprises at least one metal selected from Group VIB elements of the periodic table. Preferably, the first metal fraction comprises at least one metal selected from chromium, molybdenum or tungsten. More preferably, the first metal fraction is a single metal. Even more preferably, the first metal fraction is molybdenum. The second metal fraction comprises at least two metals selected from Group VIIIB elements of the periodic table. Preferably, the second metal fraction comprises at least two metals selected from cobalt, rhodium, iridium, palladium, or platinum. More preferably, the second metal fraction comprises at least one metal from the first metal subgroup selected from cobalt, rhodium or iridium and a second metal selected from nickel, palladium or platinum and at least one metal from the subgroup. Even more preferably, the second metal fraction comprises one metal from the first metal subgroup and one metal from the second metal subgroup. More preferably, the second metal fraction comprises cobalt and nickel.

Preferably, the combined total weight of the first metal fraction and the second metal fraction is 3.0 to 12.0 weight percent based on the total weight of the catalyst. More preferably, the total weight of the first metal fraction and the second metal fraction is 5.0-10.0 wt%. Even more preferably, the total weight of the first metal fraction and the second metal fraction is between 6.0 and 8.0 wt%.

Preferably, the first metal subgroup is present in an amount of 0.5 to 2.0 wt.%, based on the total weight of the catalyst, and the second metal subgroup is 0.5 to 2.0 wt. It is present in an amount of 3-1.0% by weight. More preferably, the first metal subgroup is present in an amount of 0.80-1.20% by weight and the second metal subgroup is present in an amount of 0.40-0.60% by weight, based on the total weight of the catalyst. %.

Preferably, it further comprises a ratio of the first metal fraction to the second metal fraction in the range of 2.0-6.0. More preferably, it further comprises a ratio of the first metal fraction to the second metal fraction in the range of 3.0-5.0. Even more preferably, it further comprises a ratio of the first metal fraction to the second metal fraction in the range of 3.5-4.5.

Catalyst preparation process

The subject catalysts are prepared by first mixing the alumina with a solvent such as water and, if the alumina is peptized, with a deflocculating liquid to form a dough-like material suitable for molding such as extrusion. prepared. Mixing is typically done in a low energy mixer or high energy mixing device to combine these components. The dough-like carrier material is then extruded, dried and calcined. Finally, the dried/calcined extrudate is impregnated with the metal component.

deflocculation

Peptization of alumina is a process used to break down large alumina particles into smaller particles by chemical treatment to make a suitable binder for catalyst compositions. Peptizers, which can contain acids and water, also affect the pore structure of the catalyst and can be used to adjust the pore size distribution. The acid used to peptize the alumina is preferably selected from monobasic acids. More preferably, the acid is selected from the group consisting of formic acid, nitric acid, hydrochloric acid, acetic acid, and mixtures thereof. Even more preferably, the acid used to peptize the alumina is hydrochloric acid or nitric acid. Most preferably, deflocculation is carried out using nitric acid. Peptization of alumina is preferably carried out using 1.0 to 4.0 weight percent acid in the peptization process. More preferably, 1.5-3.5% by weight is used. Most preferably, 2.0-3.0 wt% is used. Preferably, an aqueous solution of acid, water, and uncalcined pseudoboehmite alumina is fed to a mixer and mixed to achieve a water content of 50 to 65 weight percent as determined by loss on ignition measurement in air at 1750°F. Creates a dough-like material with modulus. The mixed solids are then formed into catalyst particles having the desired size and shape, as described below.

Extrusion/drying

After the alumina has been peptized, the resulting dough-like material is first extruded to form extrudates in equipment known in the art such as ram extruders, single screw extruders or twin screw extruders. do. After extrusion, the extrudate can be dried at a temperature of 100-200° C. for 10 minutes-48 hours or calcined at 400-900° C. for 0.5-48 hours. The extrudates may also be dried as above and subsequently calcined as above. Preferably, the shape of the dried/calcined extrudates comprises square prisms, cylinders, trilobes, or tetralobes. Preferably, the extrudate diameter is between 0.2 and 10.0 mm. More preferably, the diameter of the extrudate is 0.8-3.0 mm.

Following drying/calcination, the active metal is impregnated into the support by contacting the metal-containing solution with the support such that the metal is deposited in the pores of the support. A metal-containing solution can be prepared by dissolving a metal compound in a solvent in which the metal compound is preferably present as an oxide, nitrate, or carbonate. The metals in the metal-containing solution can be impregnated by any method known in the art. Preferably, metal impregnation is performed by the incipient wetness impregnation method. In this impregnation method, the amount of active metal deposited on the carrier can be controlled by adjusting the concentration of the active metal in the solution or the amount of solution used.

After impregnation, the impregnated support can be dried at a temperature of 100-200° C. for a period of 10 minutes to 48 hours, or calcined at a temperature of 400-700° C. for a period of 0.5-48 hours. can. Preferably, the impregnated support can be first dried and then calcined as described above. Preferably, the metal of the first metal fraction is impregnated separately from the second metal fraction, wherein the separate impregnations are separated by drying and/or calcination steps.

Alternatively, the metal can be impregnated into the support by adding a metal-containing solution to the alumina in a peptization step using acid and water. The resulting material is extruded, dried and optionally calcined as described above.

Catalyst pore size distribution

Preparation of the catalyst as described above results in a specially designed pore volume distribution, with the largest proportion of the pore volume being in pores with diameters less than 12-16 nm and An intermediate amount of volume has a diameter of less than 2-12 nm, and a minimum amount of pore volume from pores has a diameter of 16+ nm (ie, pores are 16 nm or greater). Combined with the trimetallic design, the overall structure of the pore size network, represented by the combination of specified levels of pore volume in these particular pore size ranges, favors the catalytic activity of smaller pores. and the ability to accumulate metals to prevent pore blockage in favor of larger pores.

Unless otherwise specified, pore volume and distribution, and catalyst surface area are determined by the methods described below.

As used herein, "total pore volume" means the cumulative volume in cc/g of all pores discernible by nitrogen desorption. For catalyst supports or support particles, particularly alumina powder, the pore size distribution and pore volume are determined according to E.M. P. Barrett, L. G. Joyner and P.S. P. Halenda (“BJH”), “The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms,” J. Am. Am. Chern. Soc. , 1951, 73(1), pp 373-380 with reference to nitrogen desorption isotherms (assuming cylindrical pores). can.

The total nitrogen pore volume of the sample is the sum of the nitrogen pore volumes determined by the nitrogen desorption method and BJH calculations described above.

"Surface area" as used herein is defined by S.W. Brunauer, P.; Emmett, and E.M. It refers to the specific surface area determined by nitrogen adsorption using the BET technique as described above by Teller in the Journal of The American Chemical Society, 60(2), pp 309-319 (1938).

All morphological properties including weight such as pore volume, PV (cc/g) or surface area, (SA) (m ² /g) were measured against metal-free standards according to procedures known in the art. can be normalized. However, the morphological properties published herein are based on "actual measurement" standards that are not corrected for metal content.

Total volatiles (TV) of alumina was measured by loss on ignition in air at 1750°F. Na ₂ O was measured by ICP atomic emission spectroscopy or X-ray fluorescence.

Pores less than 12 nm (2 nm to <12 nm)

The pore volume of the pores in the catalyst with a pore diameter of less than 12 nm, ie between 2 nm and less than 12 nm, is typically between 0.15 mL/g and less than 0.28 mL/g. For the purposes of this specification, pore volumes in the range of 2 nm to <12 nm are referred to as secondary pore volumes. Preferably, the pore volume is between 0.16 and 0.25 mL/g, more preferably between 0.17 and 0.22 mL/g. Pore volumes in the range of 2 nm to <12 nm are typically 20.0-45.0%, preferably 22.0-37.0%, more preferably 25.0-32.0% of the total pore volume. Represents 0%.

Pores from 12 nm to <16 nm

The pore volume of pores in the catalyst with pore diameters between 12 nm and <16 nm is typically between 0.28 mL/g and less than 0.45 mL/g. For the purposes of this specification, the pore volume in the range of pores from 12 nm to <16 nm is referred to as the first pore volume. Preferably, the pore volume is 0.30-0.40 mL/g. More preferably, the pore volume is between 0.32 and 0.36 mL/g. The pore volume with pore diameters from 12 nm to <16 nm is typically 37.0-75.0% of the total pore volume, preferably 42.0-60.0%, more preferably 47.0- 53.0%.

12-60 nm pores

Typically, the pore volume of the pores in the catalyst with pores having a pore size of 12-60 nm is 0.32 mL/g to 0.60 mL/g. Preferably, the pore volume of the pores is between 0.42 mL/g and 0.55 mL/g. More preferably, the pores have a pore volume of 0.46 to 0.52 mL/g. Typically, pore volumes in the range 12 nm to 60 nm constitute 53.0-80.0% of the total pore volume. Preferably, the pore volume in the range 12 nm-60 nm constitutes 60.0-77.0% of the total pore volume. More preferably, the pore volume in the range 12 nm-60 nm constitutes 67.0-74.0% of the total pore volume.

16-60 nm pores

Typically, the pore volume of pores in the catalyst with pore sizes between 16 nm and 60 nm is between 0.01 mL/g and 0.20 mL/g. For the purposes of this specification, the pore volume in the 16-60 nm range is referred to as the tertiary pore volume. Preferably, the pore volume in this range is from 0.02 mL/g to 0.19 mL/g. More preferably, the pore volume in this range is 0.10-0.18 mL/g. The pore volume in the range 16 nm-60 nm constitutes 1.0-28.0%, preferably 8.0-27.0%, more preferably 15.0-26.0% of the total pore volume .

total pore volume

The total pore volume of the hydrotreating catalyst is typically 0.63-0.75 mL/g. Preferably, the total pore volume is 0.64-0.74 mL/g. More preferably, the total pore volume is 0.65-0.73 mL/g.

Surface area

The specific surface area (SA) of the subject hydroprocessing catalysts is typically 180-230 m ² /g. Preferably, the specific surface area is 185-225 m ² /g, more preferably 190-220 m ² /g.

phosphorus content

Preferably, the hydroprocessing catalyst contains a maximum phosphorus content of 1000 ppm based on the total mass of the hydroprocessing catalyst. More preferably, the maximum phosphorus content of the hydrotreating catalyst is 200 ppm. If the hydrotreating catalyst contains higher amounts of phosphorus, the resulting metal deposition on the catalyst may be too high, thereby plugging the pore mouths of the catalyst.

Median pore diameter (MPD)

Preferably, the median pore size of the subject hydroprocessing catalysts is between 10.0 and 16.0 nm. Preferably, the median pore size is between 11.0 and 15.0 nm. More preferably, the median pore diameter is between 13.4 and 14.3 nm. For the purposes of this specification, median pore size means the pore size in which half of the pore volume distribution is within the larger pore size according to the pore size distribution.

The following examples further illustrate the performance of the process of the invention. Those skilled in the art will recognize numerous modifications that are within the spirit of the invention and scope of the claims.

In the examples, catalytic activity tests were performed using a Middle Eastern feedstock as described in the procedure given below. The characteristics of the Middle East feedstock are:

Sulfur content C _S0 : 2.1% by mass, measured according to JIS K2541.

Vanadium content _CV0 : 15.0 mass ppm, measured according to JIS K0116.

Nickel content C _Ni0 : 7.0 mass ppm, measured according to JIS K10116.

Example 1

The hydrotreating catalyst of Example 1 was prepared by first using a nitrogen pore volume of 1.02 cc/g, a surface area of 350 m ² /g, a Na ₂ O content of 0.05 wt. It was carried out by adding nitric acid and water to a raw material powder containing pseudo-boehmite alumina, having 0% by weight, to obtain a carrier dough, and then kneading. 2.0 wt% _HNO3 was used, based on the total weight of the carrier mass (alumina, acid and water). An extrudate was obtained by extruding the obtained dough. The resulting extrudates were dried at 130°C for 18 hours and then calcined at 800°C for 1 hour. The obtained carrier was impregnated with an ammonium molybdate solution obtained by dissolving molybdenum trioxide (MoO ₃ ) in an ammonia solution. The percentage of molybdenum in the final catalyst is as shown in Table 1. The carrier was dried at 130° C. for 18 hours. A solution containing nickel nitrate and cobalt nitrate was prepared and then impregnated onto a dry support to produce a catalyst with cobalt and nickel content in the final catalyst as shown in Table 1. The support impregnated with the nickel and cobalt solution was then dried at 130° C. for 18 hours. The dried support was calcined at 450°C for 25 minutes to produce the catalyst.

The molybdenum, nickel, and cobalt contents in the catalyst of Example 1 were determined by ICP emission spectrochemical analysis and are shown in Table 1. The pore size distribution, specific surface area and median pore size of the pores of the catalyst of Example 1 were measured by the methods described above. Table 1 shows the results.

Catalytic activity test procedure

Experiments were conducted to test the hydrodesulfurization (HDS), hydrodemetalization (HDM), hydrodenickel (HDNi) and hydrodelysis (HDV) activities of Example 1. A fixed bed reactor was packed with the catalyst of Example 1. The catalyst was contacted with a stream of hydrogen gas and a Middle East feedstock under the following conditions.

Hydrogen partial pressure -14.0Mpa

Liquid hourly space velocity (LHSV) -1.6h ^-1

Hydrogen gas to oil ratio - 928 Nm ³ /m ³

The fixed bed reactor was continuously maintained at four different temperatures: 340°C, 360°C, 380°C and 390°C. At each temperature, the concentrations of sulfur (C _s ), vanadium (C _v ), and nickel (C _Ni ) in the product oil were measured using the methods previously described. HDM (Equation 1A), HDNi (Equation 1B), HDV (Equation 1C) at each temperature where C _V0 and C _Ni0 are the concentrations of vanadium and nickel in the feed oil, assuming first order kinetics in a plug flow reactor. The kinetic constants of the reactions were calculated. The kinetic constants of HDS are calculated at each temperature assuming secondary reaction kinetics in a plug flow reactor (equation 1D), where _CSO denotes the sulfur concentration of the feed and _d0 is the feed indicates the density of

k _HDM =LHSV ^* In[(C _V0 +C _Ni0 )/(C _V +C _Ni )] (equation 1A)

k _HDNi = LHSV ^* In[C _Ni0 /C _Ni ] (equation 1B)

k _HDV = LHSV ^* In[C _V0 /C _Vi ] (equation 1C)

k _HDS =LHSV/(C _S0 ^* d ₀ /3.208) ^* (C _S0 /C _S −1) (equation 1D)

Using the Arrhenius equation (Equation 2), the inverse absolute temperature (1/T) where temperature is in Kelvin, using the natural logarithm of the rate constant (obtained from Equations 1A-1D), and the least squares method Plotted against the calculated best fit regression line. Using these regression lines, calculated reaction rate constants (k _i,c ) at 380° C. were calculated for each reaction type (HDM, HDNi, HDV and HDS) for each sample. See, for example, Tables 2 and 3.

lnk=−(E/R) ^* (1/T)+lnA (equation 2)

During the ceremony,
k = each individual reaction (HDM, HDNi, HDV
or HDS) E = activation energy R = gas constant A = frequency factor T = temperature, Kelvin

For ease of comparison, the relative reaction activity was calculated for each example catalyst and is shown in Table 1 as a percentage. These relative activities are calculated by dividing the calculated rate constant (k _i,c ) for each example by the calculated rate constant for the reference case. All samples were tested for catalytic activity as in Example 1 unless otherwise stated. The estimated rate constants for the reference case were as above, except that the fixed bed reactor was packed with two layers of a 60:40 mixture by weight of the catalyst of Comparative Example 1 followed by the catalyst of Comparative Example 2. Measured. By definition, the relative activity of the reference case is 100%. See, for example, Tables 2 and 3.

Example 2

In Example 2, the preparation of the hydrotreating catalyst was carried out in the same manner as in Example 1, except that alumina powder Versal 250, commercially available from UOP, was used. Versal 250 has a nitrogen pore volume of 0.82 cc/g, a surface area of 350 ^m2 /g, a _Na2O content of 0, and a volatility of 25.0 wt%. Additionally, 3.0 wt% _HNO3 was utilized in the preparation, based on the total weight of the carrier mass (alumina, acid and water). The hydrotreating tests and catalyst characterization of Example 2 were carried out in the same manner as in Example 1. Table 1 shows the results. Finally, in the same manner as in Example 1, the demetallizing activity, HDNi activity, HDV activity, HDNi activity/HDV activity, and desulfurization activity of Example 2 were measured. Table 1 shows the results.

Example 3

The hydrotreating catalyst of Example 3 has a nitrogen pore volume of 0.99 cc/g, a surface area of 350 m ² /g, a Na ₂ O content of 0.05 wt %, and a volatility of 32.0 wt % Prepared in the same manner as in Example 1, except that pseudoboehmite alumina powder was used. Additionally, 2.0 wt% _HNO3 was utilized in the preparation, based on the total weight of the carrier mass (alumina, acid and water). The hydrotreating tests and catalyst characterization of Example 3 were carried out in the same manner as Example 1, except for changing the hydrotreating catalyst. Table 1 shows the results. Finally, in the same manner as in Example 1, the demetallizing activity, HDNi activity, HDV activity, HDNi activity/HDV activity, and desulfurization activity of Example 3 were measured. Table 1 shows the results.

Comparative example 1

The hydrotreating catalyst of Comparative Example 1 was produced using the alumina powder according to Example 2 and the support according to Example 1 was prepared. Additionally, 0.5 wt% _HNO3 was utilized in the preparation, based on the total weight of the carrier mass (alumina, acid and water). The carrier was then impregnated with an ammonium molybdate solution as described in Example 1 to produce the molybdenum content shown in Table 1. After drying, the molybdenum impregnated support was then impregnated with nickel using a nickel nitrate solution as described in Example 1 to produce catalysts with nickel contents as shown in Table 1. No cobalt was impregnated onto the carrier. The carrier was dried at 130°C for 18 hours and then calcined at 450°C for 25 minutes. The hydrotreating tests and catalyst characterization of Example 1 were carried out in the same manner as in Example 1, except for changing the hydrotreating catalyst. Table 1 shows the results. Finally, the desorption of Comparative Example 1 was performed in the same manner as in Example 1, except that the fixed bed reactor was charged with a 60:40 two-layer mixture by weight of Comparative Example 1 followed by Comparative Example 2. Metal activity, HDNi activity, HDV activity, HDNi activity/HDV activity, and desulfurization activity were measured. Table 1 shows the results.

Comparative example 2

The catalyst of Comparative Example 2 is pseudoboehmite alumina having a nitrogen pore volume of 0.94 cc/g, a surface area of 350 m ² /g, a Na ₂ O content of 0.05 wt %, and a volatility of 34.0 wt %. It was produced in the same manner as Example 1, except that powder was used. Carrier calcination was performed at 740°C. Additionally, 4.0 wt% _HNO3 was utilized in the preparation, based on the total weight of the carrier mass (alumina, acid and water). The testing and characterization of the catalyst of Comparative Example 2 was also the same as in Example 1. Table 1 shows the results. Finally, the desorption of Comparative Example 2 was performed in the same manner as in Example 1, except that the fixed bed reactor was charged with a 60:40 two-layer mixture by weight of Comparative Example 1 followed by Comparative Example 2. Metal activity, HDNi activity, HDV activity, HDNi activity/HDV activity, and desulfurization activity were measured.

Comparative example 3.

The hydrotreating catalyst of Comparative Example 3 was prepared similarly to Comparative Example 1 except that the peptization conditions were adjusted and the impregnation conditions were adjusted to achieve the molybdenum and nickel concentrations in Table 1. No cobalt was impregnated into the carrier. Additionally, 3.0 wt% _HNO3 was utilized in the preparation, based on the total weight of the carrier mass (alumina, acid and water). Testing and characterization of the catalyst of Comparative Example 3 was also similar to Example 1. Table 1 shows the results. Finally, in the same manner as in Example 1, the demetallizing activity, HDNi activity, HDV activity, HDNi activity/HDV activity, and desulfurization activity of Comparative Example 3 were measured.

Comparative example 4

The hydrotreating catalyst of Comparative Example 4 was prepared similarly to Comparative Example 1 except that the alumina of Example 3 was used. Additionally, 2.0 wt% _HNO3 was utilized in the preparation, based on the total weight of the carrier mass (alumina, acid and water). Hydrotreating tests and catalyst characterization of Comparative Example 4 were carried out in the same manner as in Example 1. Table 1 shows the results. Finally, in the same manner as in Example 1, the demetallizing activity, HDNi activity, HDV activity, HDNi activity/HDV activity, and desulfurization activity of Comparative Example 4 were measured. Table 1 shows the results.

Comparative example 5

The hydrotreating catalyst of Comparative Example 5 was prepared similarly to Comparative Example 3 except that the alumina of Example 3 was used. Additionally, 2.0 wt% _HNO3 was utilized in the preparation, based on the total weight of the carrier mass (alumina, acid and water). The hydrotreating test for Comparative Example 5 was also carried out in the same manner as for Comparative Example 3. Characterization of the hydrotreating catalyst of Comparative Example 5 was carried out in the same manner as in Example 1. Table 1 shows the results. Finally, in the same manner as in Example 1, the demetallizing activity, HDNi activity, HDV activity, HDNi activity/HDV activity, and desulfurization activity of Comparative Example 5 were measured. Table 1 shows the results.

Comparative example 6

The hydrotreating catalyst of Comparative Example 6 was prepared similarly to Comparative Example 1 except that the alumina of Example 1 was used. Additionally, 0.5 wt% _HNO3 was utilized in the preparation, based on the total weight of the carrier mass (alumina, acid and water). Hydrotreating tests and catalyst characterization of Comparative Example 6 were carried out in the same manner as in Example 1. Table 1 shows the results. Finally, in the same manner as in Example 1, the demetallizing activity, HDNi activity, HDV activity, HDNi activity/HDV activity, and desulfurization activity of Comparative Example 6 were measured. Table 1 shows the results.

As shown in Table 1, the hydrotreating catalysts of Examples 1-3 were confirmed to demonstrate superior performance in demetallization and desulfurization activity compared to the catalysts of Comparative Examples 1-6. The examples of the invention demonstrate higher relative HDS activity than the comparative examples. Additionally, nickel, which is generally more difficult to remove than vanadium, is removed with significantly higher selectivity and activity in the inventive examples than in the comparative examples.

Other features, advantages and embodiments of the invention disclosed herein will become readily apparent to those skilled in the art after reading the foregoing disclosure. In this regard, although specific embodiments of the invention have been described in considerable detail, alterations and modifications of these embodiments can be affected without departing from the spirit and scope of the invention as described and claimed. .

Claims (36)

A hydrotreating catalyst comprising a support and a metal component impregnated in the support,
- said support comprises alumina,
- said metal component comprises a first metal fraction and a second metal fraction, said first metal fraction comprising at least one metal selected from chromium, molybdenum or tungsten; the two metal fractions comprise at least two metals selected from cobalt, rhodium, iridium, nickel, palladium, or platinum;
The catalyst has a first pore volume of 0.28 to 0.45 mL/g for pores with pore sizes of 12 nm to less than 16 nm, and for pores of 2.0 nm to less than 12.0 nm. A catalyst having a secondary pore volume of 0.15-0.28 mL/g. 2. The catalyst of claim 1, further comprising a weight ratio of said first metal fraction to said second metal fraction in the range of 2.0 to 6.0. Catalyst according to claim 2, wherein said weight ratio ranges from 3.0 to 5.0. Catalyst according to claim 3, wherein said weight ratio is in the range of 3.5 to 4.5. wherein said second metal fraction comprises at least one metal from a first metal subgroup selected from cobalt, rhodium, or iridium and from a second metal subgroup selected from nickel, palladium, or platinum; and at least one metal of The first metal subgroup is present in an amount of 0.5-2.0 wt% based on the total weight of the catalyst and the second metal subgroup is 0 based on the total weight of the catalyst. A catalyst according to claim 5, present in an amount of .3 to 1.0% by weight. The first metal subgroup is present in an amount of 0.80 to 1.20 wt% and the second metal subgroup is present in an amount of 0.40 to 0.60 wt%, based on the total weight of the catalyst. 7. The catalyst of claim 6 present in an amount of %. 6. The catalyst of claim 5, wherein said second metal fraction comprises one metal from said first metal subgroup and one metal from said second metal subgroup. Catalyst according to claim 1, wherein the total weight of said first metal fraction and said second metal fraction is from 3.0 to 12.0 wt% based on the total weight of said catalyst. Catalyst according to claim 9, wherein the total weight of said first metal fraction and said second metal fraction is from 5.0 to 10.0 wt%. Catalyst according to claim 10, wherein the total weight of said first metal fraction and said second metal fraction is from 6.0 to 8.0 wt%. Catalyst according to claim 1, wherein the first metal fraction is molybdenum. 2. The catalyst of claim 1, wherein said second metal fraction comprises cobalt and nickel. Catalyst according to claim 1, wherein the metal components comprise molybdenum, cobalt and nickel. Catalyst according to claim 1, wherein the first pore volume is between 0.30 and 0.40 mL/g. 16. The catalyst of claim 15, wherein said first pore volume is between 0.32 and 0.36 mL/g. Catalyst according to claim 1, wherein said second pore volume is between 0.16 and 0.25 mL/g. Catalyst according to claim 17, wherein the second pore volume is between 0.17 and 0.22 mL/g. The catalyst of claim 1, further comprising a third pore volume of 0.01-0.20 mL/g for pores of 16 nm-60 nm. 20. The catalyst of claim 19, wherein said third pore volume is between 0.02 and 0.19 mL/g. 21. The catalyst of claim 20, wherein said third pore volume is between 0.10 and 0.18 mL/g. 20. The catalyst of claim 19 , wherein the sum of said first pore volume and said third pore volume is between 0.32 and 0.60 mL/g. 23. The catalyst of claim 22, wherein the sum of said first pore volume and said third pore volume is between 0.42 and 0.55 mL/g. 24. The catalyst of claim 23, wherein the sum of said first pore volume and said third pore volume is between 0.46 and 0.52 mL/g. The catalyst of claim 1, further comprising a total pore volume of 0.63-0.75 mL/g. 26. The catalyst of claim 25, having a total pore volume of 0.64-0.74 mL/g. 27. The catalyst of claim 26, having a total pore volume of 0.65-0.73 mL/g. Catalyst according to claim 1, further comprising a specific surface area of 180-230 m ² /g. Catalyst according to claim 28, wherein the specific surface area is between 185 and 225 m ² /g. A catalyst according to claim 29, wherein said specific surface area is between 190 and 220 m ² /g. The catalyst of claim 1, further comprising a median pore size of 10.0-16.0 nm. 32. The catalyst of claim 31, wherein said median pore size is between 11.0 and 15.0 nm. 33. The catalyst of claim 32, wherein the median pore size is 13.4-14.3 nm. 2. The catalyst of claim 1, further comprising a maximum phosphorus content of 1000 ppm based on the total weight of said catalyst. 35. A catalyst according to claim 34, wherein said maximum phosphorus content is 200 ppm. 1. A process for producing a hydroprocessing catalyst comprising impregnating a metal component onto a support,
- said support comprises alumina,
- said metal component comprises a first metal fraction and a second metal fraction, said first metal fraction comprising at least one metal selected from chromium, molybdenum, tungsten, or mixtures thereof; wherein said second metal fraction comprises at least two different metals selected from cobalt, rhodium, iridium, nickel, palladium, platinum, or mixtures thereof;
The catalyst has a first pore volume of 0.28 to 0.45 mL/g for pores with pore sizes of 12 nm to less than 16 nm, and for pores of 2.0 nm to less than 12.0 nm. A process having a secondary pore volume of 0.15-0.28 mL/g.